International Journal of General Engineering

and Technology (IJGET)

ISSN: 2278-9928
Vol.1, Issue 2 Nov 2012 9-18
© IASET

PROPERTIES OF LOW DENSITY POLYETHYLENE (LDPE) / EGGSHELL POWDER

(ESP) COMPOSITES: THE EFFECT OF ETHYLENE DIAMINE-ISOPTHALIC ACID

A.G. SUPRI & SITI SHUHADAH

Division of Polymer Engineering, School Of Material Engineering, Universiti Malaysia Perlis (Unimap), 02600 Jejawi,
Perlis, Malaysia

ABSTRACT

`The effect of ethylene diamine-isophthalic acid on tensile properties, morphology properties, water absorption,
and thermal properties of the low density polyethylene/eggshell powder composites were studied. The both composites,
low density polyethylene/eggshell powder (LDPE/ESP) and low density polyethylene / modified eggshell powder
(LDPE/ESPM) composites were prepared with Z-Blade Mixer at 1800C and rotor speed of 50 rpm. The results indicate that
the addition of ethylene diamine-isophthalic acid increased the tensile strength, Young’s modulus, glass transition
temperature (Tg), melting temperature (Tm), and water absorption resistance but lower percentage of crystallinity and the
elongation at break of the LDPE/ESP composites. The micrographs of SEM showed that the eggshell powder was more
widely dispersed in the LDPE matrix with the addition of ethylene diamine-isophthalic acid as a coupling agent.

KEYWORDS: Low Density Polyethylene, Ethylene Diamine-Isophthalic Acid, Eggshell Powder

INTRODUCTION

In recent decades, growing environmental awareness has resulted in renewed interest in the use of natural
materials for different applications. Increasingly more stringent environmental policies have forced industries such as the
automotive, packaging and construction industries to search for new materials that can substitute traditional composite
materials consisting of a plastic matrix and inorganic reinforcement [1-2].The incorporation of mineral fillers into
thermoplastics has been widely practiced in industry to extend them and to enhance certain properties. Fillers often
increase the performance of polymeric products.

The degree of improvement on the judicious choice of filler origin, particle size and shape, the fraction of filler,
and the surface treatment promoting interaction between the polymer matrix and filler [3]. The addition of fillers to
polymers is a fast and cheap method to modify the properties of the base materials. For this reason, particulate filled
polymers have been, and are, a subject of increasing interest in both industry and research. In this way, strength, stiffness,
electrical and thermal conductivity, hardness and dimensional stability, among other properties can be tailored to the
required values. The modification of the interfacial and interphase properties of polymer composites is mainly carried out
in order to achieve a certain degree of compatibilization in the system.

As described before, there are two ways to improve mechanical properties through the use of filler: by changing
its particle size and by treating it with coupling agents [4]. Scanning electron microscopy (SEM) is routinely used for
morphology investigation of polymer blends and composites. Sample surface is observable by the SEM method and the
elements of the structure can be identified. A study of the surface after fracture is a frequently used mode of sample
preparation in SEM study of polymer morphology [5]. This article reports that an investigation on the mechanical
10 A.G. Supri & Siti Shuhadah

properties, thermal properties, water absorption, and morphology of unmodified (ESP) and modified eggshells powder
(ESPM) into low density polyethylene / eggshell powder composites.

MATERIALS AND EXPERIMENTAL

Materials

Low density polyethylene (LDPE) grade L705 (MFI 7g/10 min and density 0.918 g/cm3) was obtained from
Polyolefins Company, Singapore. The eggshell was obtained from local market. Ethanol (C2H5 OH), sodium hydroxyl
(NaOH), ethylene diamine, and isophthalic acid with Mr 166.14 were supplied from Sigma-Aldrich Chemie GmbH,
Penang, Malaysia.

Preparation of Eggshell Powder

Eggshells were washed, dried and grinded. Eggshell was grinded to powder using the blender. Sieve was used to
obtain an average filer sizes of 63 µm. Eggshell Powder was dried in vacuum oven at 800C till the constant weight is
occurred to make it free from moisture. After that the Eggshells Powder were examined using the X-ray fluorescene
spectrometer as shown in Table 1.

Treated the Eggshell Powder

Eggshell powder has been average sizes of 63 µm was treated by using the sodium hydroxide (NaOH). The
eggshell powder was mixed with the solution of 10% NaOH. The eggshell powder was mixed with the solution and stirred
for 6 minutes at room temperature until two layers is formed. The upper layer is decanted and the deprotenized layer that
is precipitate is washed with distilled water. The wash precipitated sample is dried in the oven at 1050C till the constant
weight obtained
Modified the Eggshell Powder
Chemical modification of modified eggshell powder was carried out by adding ethylene diamine-isophthalic acid
and ethanol. The eggshell powder was dipped in an ethanol solution containing ethylene diamine-isophthalic acid (6% by
weight of ESP) at 48 hours at 500C. The eggshell powder then decanted and dried in an air oven at temperature of 700C for
2 hours.
Composite Preparation

The formulation of low density polyethylene/eggshell powder (LDPE/ESP) composites and low density
polyethylene /modified eggshell powder (LDPE/ESPM) is given in Table 1. The Z-Blade mixer was set at temperature of
180ºC and a rotor speed of 50 rpm. Low density polyethylene was then charged into Z-blade mixer to start the melt mixing.
LDPE was preheated for 20 minutes in the mixing chamber. Next, eggshell powder (ESP) or modified eggshell powder
(ESPM) are added to the soften LDPE. The mixing process was allowed for another 5 minutes in order to obtain
homogeneous composites. The composites was discharged from the mixing chamber and pressed into thick round pieces.
The discharged composites were then allowed to cool.

Compression Molding

Samples of LDPE/ESP and LDPE/ESPM composites were compressed via an electrical heated hydraulic press to
produce the composites in plate form. The hot press machine was set at the temperature of 180ºC for both top and bottom
platen. Then, the composites were put into the mould, preheated for 8 minutes followed by compression for 4 minutes at
the same temperature and subsequently cooled under pressure for 4 minutes.
Properties of Low Density Polyethylene (Ldpe) / Eggshell Powder (ESP) 11
Composites: The Effect of Ethylene Diamine-Isopthalic Acid

Mechanical Properties Test

Tensile properties were determined according to ASTM D638 by using the Instron 5569. Dumb-bell shaped
specimens were conditioned at ambient temperature (25 + 3) 0C and relative humidity (30 + 2) % before testing. A cross
head speed of 50mm/min was used. The average of five samples was used during the test.

Scanning Electron Microscopy

Studies on morphology of the tensile fracture surface of LDPE/ESP composites and LDPE/ESPM composites
were carried out using a scanning electron microscopy (SEM) using SEM, model JEOL JSM 6460LA. Surfaces of the
samples were coated with a thin palladium layer of about 12 µm thickness using Auto Fine Coater, model JEOL JFC 1600.

Water Absorption Test

Water absorption test was carried out according to ASTM standard D750-95.It involved total immersion of three
samples in distilled water at room temperature. All the specimens were previously dried in an oven at 50 0C for 24 h and
stored in desiccators. The water absorption was determined by weighing the samples at regular interval. A Mettler balance
type AJ150 was used with a precision of + 1 mg. The percentage of water absorption (Mt) was calculated by:

W N  Wd
Mt  x100% (1)
Wd

Where Wd and WN are original dry and weight after exposure respectively. The average reading of three samples was
taken.

Differential Scanning Calorimetry Analysis

Thermal analysis measurements of selected system were performed using a Perkin Elmer DSC-7 analyzer.
Samples of about 4 mg were heated from 25 to 2500C using a nitrogen air flow of 50 ml/min and heating rate of
100C/min.The melting and crystallization behavior of selected composites also performed using a Perkin Elmer DSC-7
analyzer. The % crystallinity of composites was determined using the following relationship;

% Crystallinity   H f x 100% (2)

H  f

Where ΔHf and ΔHof are enthalpy of fusion of the composite and enthalpy of fusion of LDPE, respectively. The value for
ΔH of (LDPE) is 293.6J/g

RESULTS AND DISCUSSION

Mechanical Properties

Figure 1 shows the tensile strength of LDPE/ESP and LDPE/ESPM composites with different filler loading. It can
be seen that the tensile strength of the both composites decreases with increasing the filler loading. The decreases of tensile
strength were due to the poor adhesion of filler-matrix and agglomeration of filler particles. At similar filler loading, the
tensile strength of LDPE/ESPM composites is higher than LDPE/ESP composites.

This is probably because of a better interfacial adhesion between the filler and the matrix after chemical
modification was done. Strong adhesion between filler and matrix interface cause batter stress transfer from matrix into the
filler leads to a higher tensile strength [6]. Ethylene diamine-isopthalic acid reacts with the surface of the inorganic and
12 A.G. Supri & Siti Shuhadah

forming bonds. The usage of coupling agent was proven effective in entering the dispersion; adhesion and compatibility of
system consist of a hydrophilic filler and hydrophobic matrix.

Figure 2 shows the elongation at break of LDPE/ESP and LDPE/ESPM composites with different filler loading. It
can be seen that the elongation at break of the composites decreases with increasing filler loading. Increased the filler
loading in the LDPE matrix resulted in composite becoming stiffer and harder. This will reduce the composite resilience
and toughness and lead to lower elongation at break [7]. Figure 2 also shows the elongation at break of LDPE/ESPM
composites is lower than LDPE/ESP composites. This observation was due to the stiffness of the composites increased
gradually with associated decrease in elongation at break.

Figure 3 shows the Young’s modulus of LDPE/ESP and LDPE/ESPM composites with different filler loading.
Generally an increase in Young’s Modulus indicates that the stiffness of all samples increased. As expected, the Young’s
Modulus, which indicates the material stiffness increases steadily with filler content. This is because at high filler loading
the composite will be able to withstand more loads.

The original purpose of the incorporation of fillers, especially the particulate filler, into the polymer matrix is to
improve the modulus of the resulting composites. Young’s modulus of the composites is affected by the filler modulus,
filler loading, and filler aspect ratio [8]. LDPE/ESPM composites had a higher Young’s modulus than LDPE/ESP
composites. This was due to the better interfacial interaction between filler and the polymer matrixes in LDPE/ESP
composites

Morphology Properties

Figure 4 shows the micrographs of tensile fracture of the LDPE/ESP and LDPE /ESPM composites with different
filler loading. The agglomeration and cavities tend to form as more filler were added to the LDPE matrix. Figure 4 (a,c)
indicated an extensive filler full out from the matrixes than 5 (b,d). From SEM micrographs, the eggshell modified with
ethylene diamine-isophthalic acid in Figure 5 (b,d) look well contacted in LDPE matrix with good adhesion characteristics,
which coincides with the result of the tensile strength as shown in Fig. 1.

As the amount of eggshell powder loading increases in the composites, the tendency for filler-filler interaction
increases rather than filler-matrix interaction to form agglomeration. This was due to the difficulties to achieve
homogenous dispersion of filler at higher filler loading [9-10]. This resulted in poor dispersion of filler in higher filler
loading as shown in Figure 4 (e,f). These morphological results were also well matched with the tensile strength results in
Figure 1.

Water Absorption Analysis

Figures 5 and 6 Show the percentage of water absorption versus time for LDPE/ESP composites and
LDPE/ESPM with different filler loading while Figure 7 shows the equilibrium water absorption for LDPE/ESP and
LDPE/ESPM composites. The water absorption increased with time. LDPE/ESP composites with higher eggshells powder
loading shows more water absorption. This is due to the higher contents of filler in the composites that can absorb more
water. As the filler loading increase, the formation of agglomeration is found due to the difficulties to achieve homogenous
dispersion of filler at high filler loading. The agglomeration of the filler in composites increases the water absorption of the
composites. The Figures also show the percentage of water absorption for LDPE/ESPM was lower than LDPE/ESP
composites due to the better interfacial adhesion between LDPE and ESP with the presence of ethylene diamine-
isophthalic acid as a coupling agent.
Properties of Low Density Polyethylene (Ldpe) / Eggshell Powder (ESP) 13
Composites: The Effect of Ethylene Diamine-Isopthalic Acid

Thermal Properties

Figure 8 shows the DSC curve of LDPE/ESPM composites with different filler loading whereas Table 3 shows the
glass transition temperature (Tg), melting temperature (Tm), and % crystallinity of LDPE/ESP and LDPE/ESPM composites.
From Table 3, it can be seen that the Tg and Tm of the composites increase with increasing of filler loading. Glass transition
temperature and melting temperature for LDPE/ESPM composites are higher than LDPE/ESP composites due to the better
interaction adhesion between LDPE and ESP with the presence of ethylene diamine-isophthalic acid. The result also shows
that the percentage of crystallinity of the composites increased with increasing the filler loading. This is due to increasing
composition of eggshell powder in the composites. However, the percent crystallinity of the LDPE/ESP composites
slightly decrease with the addition of ethylene diamine-isophthalic acid .

CONCLUSIONS

The addition of ethylene diamine-isophthalic acid a coupling agent into LDPE/ESP composites enhanced
interfacial adhesion between LDPE and ESP which improved the tensile strength, Young’s modulus and reduce the
percentage of water absorption of the composites as evidenced by the morphological study by SEM. The presence of
ethylene diamine-isophthalic acid has also increased the Tg and Tm of LDPE/ESP composites. The percentage of
crystallinity of LDPE/ESP composites increased with increasing filler loading but decreases with the presence of ethylene
diamine-isophthalic acid.

REFERENCES

1. Beg, M.D.H & Pickering, K.L. (2008) Reprocessing of wood fibre reinforced polypropylene composites, Part I:
Effects on physical and mechanical properties, Composites: Part A, 1-8.

2. Supri, A.G, Ismail, H, & Shuhadah, S. (2010). Effect of polyethylene grafted maleic anhydride (PE-g-MAH) on
properties of low density polyethylene / eggshell powder (LDPE/ESP) composites, Polymer Plastics Technology
and Engineering, 49 (4): 347-353.

3. Wang Y & Wang J. J. (1999). Shear yield of calcium carbonate-filled polypropylene, Polymer Engineering
Science, 39(1):190–198.

4. Jeanette Gonz-Alez a, Carmen Albano b,c,*, Miren Ichazo a, Berenice D-ıaz. (2002). Effects of coupling agents
on mechanical and morphological behavior of the PP/HDPE blends with two different CaCO3, European Polymer
Journal, 38: 2465–2475 .

5. Ivica Janigova´a,*, Viera Khunova´b, Jana Koza´nkova´b. (1999). Plasma treatment of particulate polymer
composites for analysis by scanning electron microscopy: I. Morphology of silica filled low density polyethylene,
Polymer Testing, 18 : 51–61.

6. Morreale, M, Scaffaro , R, Maio, A, La Mantia , F. L. (2007). Effect of adding wood flour to the physical
properties of a biodegradable polymer, Composites, 12.

7. Maya, J, Thomas,A, & Varghese, K. T. (2004). Mechanical properties of sisal oil palm hybrid fiber reinforced
natural rubber composites, Composite Science and Technology, 64:955-965.

8. Ismail, I, Salmah, H, & Nor Azwin, A. (2007). The effect of maleic anhydride grafted polypropylene on thermo-
oxidative ageing of paper sludge filled polypropylene diene-terpolymer composites, Proceedings of VIIth
National Symposium on Polymeric Materials, 28.
14 A.G. Supri & Siti Shuhadah

9. Kuan, C. F, Kuan, H. C, Ma, C. C, Huang, C. M. (2006). Mechanical, thermal and morphological properties of
water-crosslinked wood flour reinforced linear low-density polyethylene composites, Composites: Part A , 37 :
1696–1707.

10. Supri, A. G & Ismail, H. (2011). The effect of isophorone diisocyanate-polyhydroxyl groups modified water
hyacinth fiber (Eichhornia crassiper) on properties of low density polyethylene/acrylonitrile butadiene styrene
(LDPE/ABS) composites, Polymer Plastics Technology and Engineering, 50: 113-120.

APPENDICES

Table 1: Inorganics Compound of Eggshell Powder Investigated by Using X-Ray Fluorescene Spectrometer
Elements Concentration
(%wt)
Al2O3 0.001
SiO2 0.001
S 0.001
Cl 0.009
CaO 99.83
Cr2O3 0.003
MnO 0.001
CuO 0.001
LOI 0.153

Table 2: Formulation of LDPE/ESP and LDPE/ESPM Composites at Different Eggshell Powder Loading

LDPE Eggshell Powder

Composites Code (Wt %) (Wt %)
LDPE 100 -
LDPE/ESP5 95 5
LDPE/ESP10 90 10
LDPE/ESP15 85 15
LDPE/ESP20 80 20
LDPE/ESP25 75 25
LDPE/ESP5M 95 5*
LDPE/ESP10M 90 10*
LDPE/ESP15M 85 15*
LDPE/ESP20M 80 20*
LDPE/ESP25M 75 25*
*
Ethylene diamine-isophthalic acid was added at 6 wt % of eggshell powder

Table 3: The Data of Thermal Parameter from DSC Of LDPE/ESP and LDPE/ESPM Composites
Composites Tg Tm % Crystallinity
Code (˚C) (˚C) (%)
LDPE 46.11 107.69 28.40
LDPE/ESP5 46.63 107.57 34.90
LDPE/ESP15 46.64 107.97 35.04
LDPE/ESP25 46.89 108.33 35.50
LDPE/ESP5M 47.86 110.02 34.12
LDPE/ESP15M 48.21 110.59 34.92
LDPE/ESP25M 48.91 110.76 35.15
Properties of Low Density Polyethylene (Ldpe) / Eggshell Powder (ESP) 15
Composites: The Effect of Ethylene Diamine-Isopthalic Acid

FIGURES

16
14 LDPE

Tensile strength (Mpa)

12
10
8
6
4
2
0
0 5 10 15 20 25
Filler loading (% wt)

Figure 1: Effect of Filler Loading on the Tensile Strength of LDPE/ESP and LDPE/ESPM Composites

500
450
Elongation at break (%)

400 LDPE LDPE/ESP

350
300
250
200
150
100
50
0
0 5 10 15 20 25
Filler loading (% wt)

Figure 2: Effect of Filler Loading on Elongation at Break of LDPE/ESP and LDPE/ESPM Composites

450
Young's modulus (MPa)

400 LDPE LDPE/ESPM

350
300
250
200
150
100
50
0
0 5 10 15 20 25
Filler loading (% wt)

Figure 3: Effect of Filler Loading on the Young’s Modulus of LDPE/ESP and LDPE/ESPM Composites

(a)LDPE/ESP5 (b) LDPE/ESPM5

16 A.G. Supri & Siti Shuhadah

(c)LDPE/ESP15 (d) LDPE/ESPM15

(e) LDPE/ESP25 (f) LDPE/ESPM25

Figure 4: SEM Micrographs of Tensile Fracture Surfaces of LDPE/ESP Composites: (A)LDPE/ESP5,

(B)LDPE/ESPM5, (C)LDPE/ESP15, (D)LDPE/ESPM15 (E) LDPE/ESP25 and (F) LDPE/ESPM25.

0.5000 LDPE

LDPE/ESP5
Water absorption (%)

0.4000 LDPE/ESP1
0
LDPE/ESP1
5
0.3000

0.2000

0.1000

0.0000
0 10 20 30 40 50 60
Time(days)

Figure 5: Water Absorption Versus Time of LDPE/ESP Composites with Different Filler Loading

0.5000 LDPE/ESPM
5
Water Absorption (%)

0.4500 LDPE/ESPM
10
LDPE/ESPM
0.4000 15
LDPE/ESPM
0.3500 20
LDPE/ESPM
0.3000 25

0.2500
0.2000
0.1500
0.1000
0.0500
0.0000
0 10 20 30 40 50 60

Time(days)

Figure 6: Water Absorption Versus Time of LDPE/ESPM Composites with Different Filler Loading
Properties of Low Density Polyethylene (Ldpe) / Eggshell Powder (ESP) 17
Composites: The Effect of Ethylene Diamine-Isopthalic Acid

0.5000

Equilibrium water absorption(%)

LDPE/ESP
0.4000 LDPE/ESPM

0.3000

0.2000

0.1000

0.0000
0 5 10 15 20 25 30

Filler loading (wt%)

Figure 7: Percentage of Equilibrium water Absorption Versus Filler Loading of LDPE/ESP and LDPE/ESPM
Composites

2.5
LDPE
2 LDPE/ESPM 5
Heat flow (W/g)

1.5 LDPE/ESPM
15
1

0.5

0
29.13
36.82
47.77
58.79
69.79
80.79
91.78
102.7

135.9
124.89

146.91
157.92
168.93
179.93
190.94
113.87

Temperature (0C)

Figure 8: Differential Scanning Calorimetry Thermogram of LDPE/ESPM with Different Filler Loading